Zinc oxide-alumina-silica-based crystallized glass

ABSTRACT

A zinc oxide-alumina-silica-based crystallized glass containing zinc oxide, alumina and silica as main components, and zirconia as a nucleating agent, the main components comprising at a ratio of 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica, the main components amounting to 100% by mass in total, the nucleating agent being contained in an amount of 3-6 parts by mass based on 100 parts by mass of the main components, and at least one component selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, diphosphorus pentoxide, niobium oxide and tantalum oxide being contained as a modification component in addition to the main components and the nucleating agent.

TECHNICAL FIELD

The present invention relates to a crystallized glass suitable for use as a substrate for reflectors (reflector substrate) for reflecting lights of light source lamp, particularly, as a reflector substrate for illuminators or projector light sources.

BACKGROUND ART

In the light sources of projectors such as OHP (over head projectors) and liquid crystal projectors and illuminators such as for spot illumination, reflectors are used for reflecting lights emitted from light source lamps. The reflectors are members exposed to high temperatures resulting from generation of heat by light source lamps such as ultra-high pressure mercury lamps and are required to have a high heat resistance. Therefore, hitherto, there have been used those which comprise a reflector substrate composed of a heat-resisting glass excellent in heat resistance (e.g., PYREX (trademark) manufactured by Corning Glass Works) and a reflective film formed on the substrate.

However, recently, light source lamps used for illuminators and projector light sources tend to be increased in output and luminance, and the level of heat resistance required is further enhanced. Under the circumstances, it is attempted to use crystallized glasses superior to heat-resisting glasses in heat resistance as materials constituting reflector substrates.

For example, it has been proposed to use lithia-alumina-silica-based crystallized glasses (hereinafter sometimes referred to as “lithia-based crystallized glasses”) such as β-spodumene solid solution (β-spodumene: Li₂O—Al₂O₃-4SiO₂) and β-eucryptite solid solution (β-eucryptite: Li₂O—Al₂O₃-2SiO₂) (see, for example, Patent Document 1). Moreover, the inventors have also proposed to use baria-alumina-silica-based crystallized glasses (hereinafter sometimes referred to as “baria-based crystallized glasses”) such as celsian (BaO—Al₂O₃-2SiO₂) (see, for example, Patent Document 2).

Patent Document 1: JP-B-7-92527 Patent Document 2: JP-A-2002-109923

DISCLOSURE OF INVENTION

However, the lithia-based crystallized glass has such a problem that it has a very small thermal expansion coefficient (JIS R1618: 40-400° C.) of about 0×10⁻⁷-20×10 ⁻⁷ (/° C.) and shows excellent heat resistance, but is inferior in meltability because of its high melting point of about 1500° C. or higher. Specifically, there are difficulties that special equipments (such as melting furnace) which can stand high temperatures of higher than 1500° C. are required for melting the glass and molding the glass to make a substrate of reflector, which puts restrictions on the production conditions. On the other hand, the above-mentioned baria-based crystallized glass is low in melting point, namely, about 1450° C. and have no such problems, but their thermal expansion coefficient (JIS R1618: 40-400° C.) is about 30×10⁻⁷-45×10⁻⁷ (/° C.), and further improvement is needed in the aspect of heat resistance.

The present invention has been made in order to solve the conventional technical problems and provides a crystallized glass which has a composition different from that of the above conventional crystallized glasses and has ahigher efficiency, specificallyahigh heat resistance equivalent to that of at least baria-based crystallized glasses, preferably an excellent heat resistance equivalent to that of lithia-based crystallized glasses, and is low in melting point like the baria-based glasses and good in meltability.

As a result of intensive research conducted by the inventors, it has been found that the above object can be attained by containing a specific modification component in a zinc oxide-alumina-silica-based crystallized glass, and the present invention has been accomplished. That is, the present invention provides the following zinc oxide-alumina-silica-based crystallized glass.

[1] A zinc oxide-alumina-silica-based crystallized glass containing zinc oxide (ZnO), alumina (Al₂O₃) and silica (SiO₂) as main components, and zirconia (ZrO₂) as a nucleating agent, wherein the main components comprise 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica and the main components amount to 100% by mass in total, the nucleating agent is contained in an amount of 3-6 parts bymass based on 100 parts bymass of themain components, and at least one component selected from the group consistingof lithiumoxide (Li₂O), sodiumoxide (Na₂O), potassium oxide (K₂O), diphosphorus pentoxide (P₂O₅), niobium oxide (Nb₂O₅) and tantalum oxide (Ta₂O₅) is contained as a modification component.

[2] A zinc oxide-alumina-silica-based crystallized glass described in the above [1], wherein a crystalline phase is constituted of the main components and the main crystalline phase is zinc petallite (Zn-petallite) solid solution or β-quartz solid solution.

[3] A zinc oxide-alumina-silica-based crystallized glass described in the above [1] or [2], wherein the modification component is contained in an amount of 0.2-5.0 parts by mass based on 100 parts by mass of the main components.

[4] A zinc oxide-alumina-silica-based crystallized glass described in anyone of the above [1]-[3], wherein tin dioxide is contained in place of a part of zirconia as the nucleating agent, and the content of tin dioxide is 0.5-4 parts by mass based on 100 parts by mass of the main components.

[5] A reflector substrate which comprises the zinc oxide-alumina-silica-based crystallized glass described in any one of the above [1]-[4] and has a main body having a concave for disposing a reflective film thereon and a metallic reticulate body embedded in the main body.

[6] A reflector substrate described in the above [5], wherein the reticulate body comprises a metal mainly composed of at least one metal selected from the group consisting of nickel (Ni), cobalt (Co), stainless steel (SUS: Steel Use Stainless) and kobar.

[7] A reflector substrate described in the above [5] or [6], wherein the reticulate body comprises a metal mainly composed of at least one metal selected from the group consistingof gold (Au), platinum (Pt), silver (Ag) and copper (Cu) or has a surface film comprising the above metal.

The zinc oxide-alumina-silica-based crystallized glass (hereinafter sometimes referred to as “zinc oxide-based crystallized glass”) has a high heat resistance equivalent to that of at least baria-based crystallized glasses, an excellent heat resistance equivalent to that of lithia-based crystallized glasses depending on conditions, and is low in melting point and good in meltability like the baria-based glasses. Furthermore, it is superior in crystal stability with elapse of time under high temperature conditions as compared with lithia-based crystallized glasses and extremely small in volumetric contraction even after exposed to high temperatures for a long time.

BRIEF DESCRIPTION OF DRAWINGS

[FIG. 1] A phase diagram which shows a preferred constitutional ratio of the main components in the zinc oxide-alumina-silica-based crystallized glass of the present invention.

[FIG. 2] A graph which shows changes with elapse of time of thermal expansion coefficient of the crystallized glass of Example 50.

[FIG. 3] A graph which shows changes with elapse of time of thermal expansion coefficient of the crystallized glass of Comparative Example 14.

[FIG. 4] A side sectional view which show a general construction of a reflector substrate.

[FIG. 5] A flow diagram which shows steps (a)-(f) of molding a reflector substrate by a reflector substrate molding mold.

[FIG. 6] A side sectional view which shows a state of use of a reflector substrate.

[FIG. 7(a)] A side sectional view which show a construction of the reflector substrate of the present invention.

[FIG. 7(b)] A side sectional view which show a construction of the reflector substrate of the present invention.

[FIG. 7(c)] A side sectional view which show a construction of the reflector substrate of the present invention.

[FIG. 8] A flow diagram which shows steps (a)-(g) of molding the reflector substrate of the present invention by a reflector substrate molding mold.

DESCRIPTION OF REFERENCE NUMERALS

10, 50—reflector substrate, 12—concave, 14—bowl-shaped portion, 15—constricted portion, 16—neck portion, 17—main body, 18—inner space, 20—through hole, 22—reflective film, 24—light source lamp, 26—fixing material, 28—protective plate, 30—reflector substrate molding mold, 32—mold, 32 a—concave portion, 33—cavity, 34—core rod, 34 a—convex portion, 35—gob feeding nozzle, 36—ring, 36 a—guide hole, 38—gob, 37—cutting blade, 52—reticulate body

BEST MODE FOR CARRYING OUT THE INVENTION

The best mode for carrying out the crystallized glass of the present invention will be specifically explained below, which should not be construed as limiting the invention in any manner.

The crystallized glass of the present invention is a zinc oxide-based crystallized glass containing zinc oxide, alumina and silica as main components, and zirconia as a nucleating agent, wherein the constitutional ratio of zinc oxide, alumina and silica as main components and the content of zirconia as the nucleating agent are controlled to specific values, and furthermore a specific modification component is contained in addition to the main components and the nucleating agent.

(1) Main Components

The crystallized glass of the present invention contains zinc oxide, alumina and silica as main components. The crystal glass of such system can be expected to be low in thermal expansion coefficient and have excellent heat resistance.

Ina zinc oxide-alumina-silica-based crystallized glass, a crystalline phase is constituted of zinc oxide, alumina and silica as the main components. The crystalline phase includes zinc petallite (Zn-petallite: a mixture of Zno.Al₂O₃.3SiO₂, ZnO.2SiO₂, ZnO.Al₂O₃.8SiO₂) solid solution, β-quartz (β-quartz: SiO₂) solid solution, gahnite (gahnite: ZnO.Al₂O₃), willemite (willemite: 2ZnO.SiO₂), etc., and the thermal expansion coefficient of zinc petallite solid solution, β-quartz solid solution and willemite is relatively low while that of gahnite is conspicuously high.

Therefore, the crystallized glass of the present invention preferably contains gahnite as its crystalline phase in an amount as small as possible, and more preferably contains substantially no gahnite (contains substantially 0% by mass of gahnite), and especially preferably the main crystalline phase is zinc petallite solid solution or β-quartz solid solution. The “main crystalline phase” in the present invention means a crystalline phase having the strongest peak intensity of diffraction X-ray measured by a powder X-ray diffractometer (e.g., trademark: RINT 2500 manufactured by Rigaku Denki Co., Ltd.) at room temperature (25° C.).

In order to specifically form a zinc petallite solid solution or β-quartz solid solution in a zinc oxide-alumina-silica-based crystallized glass, it is necessary to control the constitutional ratio of zinc oxide, alumina and silica contained as main components (hereinafter referred to as “main component constitutional ratio”) to a given value. Concretely, the zinc petallite solid solution or β-quartz solid solution comprises specifically in the constitution shown by the part of oblique lines in the phase diagram of FIG. 1, namely, in the limited constitution where the main components are constituted of 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica and these components in total amount to 100% by mass.

Table 2 shows results of evaluation on crystalline phase and thermal expansion coefficient of the zinc oxide-alumina-silica-based crystallized glasses having the main component constitutional ratios shown by the marks (I)-(VII) in the phase diagram of FIG. 1. That is, zinc oxide-alumina-silica-based crystallized glasses having the main component constitutional ratios shown by the marks (I)-(VII) in FIG. 1 and containing a nucleating agent (zirconia) in an amount shown in Table 1 and a glass clarifier (antimony oxide (Sb₂O₃)) and containing no modification component were actually prepared (Reference Examples 1-7), and these crystallized glasses were evaluated on the crystalline phase based on the peak pattern of diffraction X-ray measured by a powder X-ray diffractometer at room temperature (25° C.) and the thermal expansion coefficient (average linear thermal expansion coefficient) in accordance with the method described in JIS R1618. The results are shown in Table 2.

Specifically, the crystalline phase was evaluated using a powder X-ray diffractometer having a rotating anode type target (Cu) and a graphite monochromator (trademark: RINT 2500 manufactured by Rigaku Denki Co., Ltd.) as a powder X-ray diffractometer under the conditions of X-ray source: CuKa ray, tube voltage: 50 kV, tube current: 30 mA, diffraction angle: 2θ=10°-40° and temperature: room temperature (25° C.). A crystalline phase having the strongest peak intensity of diffraction X-ray measured is taken as a main crystalline phase of the crystallized glass.

The thermal expansion coefficient was measured on measurement sample of 3 mm×3 mm×20 mm cut out from the crystallized glass in the three temperature ranges of 40-400° C., 40-600° C. and 40-800° C. in accordance with the method of JIS R1618. The heat resistance was evaluated in the following manner. When a crystallized glass having a thermal expansion coefficient at 40-400° C. of not higher than that of lithia-based crystallized glass (not higher than 20×10⁻⁷(/° C.)) was obtained, this is indicated by “0”, when a crystallized glass having a thermal expansion coefficient at 40-400° C. of not higher than that of baria-based crystallized glass (not higher than 45×10⁻⁷ (/° C.)) was obtained, this is indicated by “A”, and when only such a crystallized glass as having a thermal expansion coefficient at 40-400° C. of more than that of baria-based crystallized glass (higher than 45×10⁻⁷ (/° C.)) was obtained, this is indicated by “X”. TABLE 1 Main component Constitutional component ratio Nucleating Glass Total of (100% by mass in total) Total of agent clarifier crystallized Mark ZnO Al₂O₃ SiO₂ main components ZrO₂ Sb₂O₃ glass in (% by (% by (% by (Part by (Part by (Part by (Part by mass) mass) mass) mass) mass) mass) mass) Referential (I) 25 20 55 100 5 0.5 105.5 Exam. 1 Referential (II) 25 15 60 100 5 0.5 105.5 Exam. 2 Referential (III) 20 20 60 100 5 0.5 105.5 Exam. 3 Referential (IV) 30 15 55 100 5 0.5 105.5 Exam. 4 Referential (V) 20 25 55 100 5 0.5 105.5 Exam. 5 Referential (VI) 30 20 50 100 5 0.5 105.5 Exam. 6 Referential (VII) 25 25 50 100 5 0.5 105.5 Exam. 7

TABLE 2 Crystallizing temp. 850° C. Crystallizing temp. 875° C. Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × 10⁻⁷ (/° C.) Crystalline 10⁻⁷ (/° C.) Crystalline 40-400° C. 40-600° C. 40-800° C. phase 40-400° C. 40-600° C. 40-800° C. phase Referential 12.9 13.7 18.7 Qu(Pe) −0.7 0.5 1.1 Qu(Pe,Wi) Exam. 1 Referential 6.9 9.5 11.4 Pe 6.8 9.3 11.4 Pe Exam. 2 Referential 8.4 9.2 12.4 Qu — — — Qu Exam. 3 Referential 9.3 11.6 14.0 Pe(Wi) — — — Pe(Wi) Exam. 4 Referential 24.3 24.9 24.9 Amor- 24.3 24.9 24.9 Qu(Ga) Exam. 5 phous Referential 30.1 uncalcu- uncalcu- Amor- — — — Pe(Qu, Wi, Ga) Exam. 6 lable lable phous Referential 30.8 uncalcu- uncalcu- Amor- −2.1 −2.0 −2.8 Qu(Ga) Exam. 7 lable lable phous Crystallizing temp. 900° C. Average linear thermal expansion coefficient × Evaluation 10⁻⁷ (/° C.) Crystalline Heat 40-400° C. 40-600° C. 40-800° C. phase resistance Referential −5.1 −4.8 −3.5 Qu(Pe,Wi) ◯ Exam. 1 Referential 7.3 10.6 12.2 Pe ◯ Exam. 2 Referential −14.3 −14.3 −13.5 Qu ◯ Exam. 3 Referential — — — Pe(Wi) ◯ Exam. 4 Referential 35.4 35.3 35.2 Qu(Ga) Δ Exam. 5 Referential 0.7 4.2 7.3 Pe(Qu, Wi, Ga) ◯ Exam. 6 Referential 11.4 11.4 10.7 Qu(Ga, Wi) ◯ Exam. 7 In Column of crystalline phase, the bold letters means main crystalline phase and letters in parentheses indicate other crystalline phases, and Qu: β-quartz solid solution, Pe: zinc-petallite solid solution, Wi: willemite, and Ga: gahnite. In Column of average linear thermal expansion coefficient, “uncalculable” shows that the calculation was impossible due to the presence of transition point and yielding point on thermal expansion curve.

As shown in Table 2, in the zinc oxide-alumina-silica-based crystallized glasses having the main component constitutional ratio shown by the marks (I)-(VII) in FIG. 1, the main crystalline phases thereof were all zinc petallite solid solution or β-quartz solid solution, and the thermal expansion coefficient was not higher than that of at least baria-based crystallized glasses (30×10⁻⁷(/° C.)-45×10⁻⁷(/° C.)), and the zinc oxide-alumina-silica-based crystallized glasses which were set at proper conditions in the main component constitutional ratio and crystallizing temperature showed a small value comparable to the thermal expansion coefficient of lithia-based crystallized glasses (0×10⁻⁷ (/° C.)-20×10⁻⁷ (/° C.)).

As mentioned above, the zinc oxide-alumina-silica-based crystallized glasses in which the main components are constituted of 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica and these components in total amount to 100% by mass have a main crystalline phase of zinc petallite solid solution or P-quartz solid solution, and hence have a low thermal expansion coefficient and excellent heat resistance. Among them, the crystallized glass having the main component constitutional ratio employed in Reference Example 1 or 3 is preferred. The zinc oxide-alumina-silica-based crystallized glasses having the above main component constitutional ratios are preferred in that they have very low thermal expansion coefficient and excellent heat resistance comparable to those of lithia-based crystallized glasses, and in addition they are semitransparent glasses less in haze and easily transmit infrared rays, and hence hardly show rising of inner temperature due to heat accumulation in the case of being used as reflector substrate, and furthermore the resulting crystallized glasses are stably low in thermal expansion coefficient irrespective of production conditions such as crystallizing temperature. Moreover, the crystallized glass having the main component constitutional ratio employed in Reference Example 1 is particularly preferred in that when they are made to the reflector substrates, the difference of thermal expansion coefficient from that of reflective material to be vapor deposited can be made small and thus occurrence of cracks in the reflective material can be effectively inhibited.

In comparison with the crystallized glass having the main component constitutional ratio employed in Reference Example 1 or 3, the crystallized glass having the main component constitutional ratio employed in Reference Example 5 is somewhat higher in thermal expansion coefficient and somewhat inferior in heat resistance because gahnite is apt to be formed, and the crystallized glass having the main component constitutional ratio employed in Reference Example 2 or 4 is a hazed white opaque glass and absorbs infrared light and hence is apt to show rising of inner temperature due to heat accumulation in the case of being used as a reflector substrate and besides is difficult in finding failures such as inner defects by visual examination, and the crystallized glass having the main component constitutional ratio employed in Reference Example 6 or 7 has the possibility that the thermal expansion coefficient greatly varies depending on production conditions such as crystallizing temperature or the crystallization does not surely proceed.

It is needless to say that the crystallized glasses having these main component constitutional ratios also have thermal expansion coefficient of not higher than that of at least baria-based crystallized glass and excellent heat resistance. It has been reported that even in the case of the zinc oxide-alumina-silica-based crystallized glasses in which the main components are constituted of 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica, those which contain no modification component mentioned hereinafter are low in melting point and insufficient in meltability although they are good in heat resistance. These crystallized glasses have a problem of being inferior in moldability. Therefore, for the crystallized glass of the present invention, it is an essential requirement for the crystallized glass to contain a specific modification component referred to hereinafter.

(2) Nucleating Agent

The crystallized glass of the present invention contain zirconia as a nucleating agent. The “nucleating agent” in this specification means a substance for acceleration of precipitation of fine glass crystals.

Generally, titania (TiO₂) or the like is contained as a nucleating agent of crystallized glass while the nucleating agent in the crystallized glass of the present invention must contains zirconia. In a crystallized glass containing titania as a nucleating agent, gahnite having very high thermal expansion coefficient is readily formed, and the thermal expansion coefficient of the crystallized glass per se tends to increase and the crystallized glass is sometimes inferior in heat resistance. The crystallized glass containing zirconia as a nucleating agent is preferred because these problems are not caused.

Zirconia as the nucleating agent must be contained in an amount of 3-6 parts by mass based on 100 parts by mass of the main components. If the content is less than the above range, zirconia does not exhibit the effect as a nucleating agent and there is the possibility of crystallization of glass being insufficient, which is not preferred. If the content exceeds the above range, there is the possibility that melting of the nucleating agent before crystallization becomes difficult, which is not preferred.

The reflector substrate can be made from the crystallized glass of the present invention by preparing a glass raw material by mixing the main components, the nucleating agent and the modification component at a given ratio, melting the glass raw material to make molten glass, molding the molten glass to a desired shape, and subjecting the molded product to a heat treatment (crystallization treatment), and during the melting and molding of the glass raw material, there occur very rarely a devitrification phenomenon or an increase of surface roughness of the molded product caused by recrystallization of zirconia as the nucleating agent.

The frequency of occurrence of the above phenomena is not so high. However, the devitrification phenomenon may make the crystallized glass heterogeneous and the increase of surface roughness of the molded product may deteriorate the reflective characteristics of reflector, and hence it is preferred to inhibit occurrence of these phenomena as much as possible.

Under the circumstances, the inventors have conducted intensive investigation to find that it is effective for inhibiting recrystallization of zirconia at the steps of melting and molding of the glass raw material, and accordingly occurrence of devitrification phenomenon and increase of surface roughness of the molded product to contain tin dioxide (SnO₂) as a nucleating agent in place of a part of zirconia as a nucleating agent. That is, it is preferred that the crystallized glass of the present invention contains tin dioxide as a nucleating agent in place of a part of zirconia as a nucleating agent, and, if necessary, contains both zirconia and tin dioxide as nucleating agents in a total amount of 3-6 parts by mass based on 100 parts by mass of the main components.

In order to inhibit recrystallization of zirconia at the steps of melting and molding of the glass raw material in crystallized glass containing only zirconia as the nucleating agent, it is effective to set the content of zirconia as the nucleating agent at 3 parts by weight or less based on 100 parts by mass of the main components. However, such crystallized glass tends to be insufficient in formation of crystal nucleus due to the low content of the nucleating agent, and is sometimes inferior in crystallinity.

On the other hand, in the case of the crystallized glass containing tin dioxide as a nucleating agent in place of a part of zirconia as a nucleating agent, recrystallization of zirconia at the steps of melting and molding of glass raw material can be inhibited with maintaining the good crystallinity and in addition the melting temperature of glass can be lowered and the meltability can be improved, which is preferred.

Tin dioxide as a nucleating agent is contained in an amount of preferably 0.5-4 parts by mass, more preferably 0.5-2 parts by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect to inhibit recrystallization of zirconia by the addition of tin dioxide cannot be exhibited, which is not desired. If the content is more than the above range, tin oxide per se is apt to be recrystallized, and there is the possibility of occurrence of devitrification phenomenon and increase of surface roughness of the molded product as in the case of zirconia.

When tin dioxide as a nucleating agent is contained in place of the whole of zirconia as a nucleating agent (namely, only tin dioxide is contained as the nucleating agent), the devitrification phenomenon at the steps of melting and molding of the glass raw material and increase of surface roughness of the molded product can also be sometimes avoided. However, since formation of gahnite (very high in thermal expansion coefficient) and willemite (higher in thermal expansion coefficient than zinc petallite solid solution or β-quartz solid solution) may be brought about, the thermal expansion coefficient of the crystallized glass per se increases, sometimes causing deterioration of heat resistance.

In the crystallized glass containing tin dioxide as a nucleating agent, it is preferred that zirconia as the nucleating agent is contained in an amount of 2-3 parts by mass based on 100 parts by mass of the main components. When the content is as mentioned above, recrystallization of zirconia at the steps of melting and molding of the glass raw material can be inhibited with maintaining the good crystallinity.

Taking the above facts into consideration, the crystallized glass of the present invention most preferably contains 3 parts by mass of zirconia and 2 parts by mass of tin dioxide as nucleating agents based on 100 parts by mass of the main components. In the case of such recrystallized glass, not only the recrystallization of zirconia at the steps of melting and molding of the glass raw material can be effectively inhibited with maintaining the good crystallinity, but also the main crystalline phase can be zinc petallite solid solution or β-quartz solid solution and hence the thermal expansion coefficient is low and a heat resistance comparable to that of lithia-based crystallized glasses is exhibited.

(3) Modification Component

The crystallized glass of the present invention contains one component selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, diphosphorus pentoxide, niobium oxide and tantalum oxide as a modification component. The “modification component” in this specification means a substance which electrostatically bonds to uncrosslinked oxygen in the crystal structure formed of the main components to affect various physical properties of the glass.

Usually, the modification components include, for example, oxides of alkali metals (lithium, sodium, potassium, rubidium, cesium, and the like.), oxides of alkaline earth metals (magnesium, calcium, strontium, barium, and the like), oxides of transition metals (yttrium, vanadium, niobium, tantalum, molybdenum, and the like), oxides of nonmetals (boron, phosphorus, and the like), and furthermore bismuth oxide (Bi₂O₃), but it is necessary that the crystallized glass of the present invention contains at least one component selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, diphosphorus pentoxide, niobium oxide and tantalum oxide (hereinafter sometimes abbreviated as “6 components”) as a modification component.

The crystallized glasses containing at least one component of the above 6 components as a modification component are more stable in thermal expansion coefficient and more excellent in heat resistance, meltability and moldability than the crystallized glasses containing no above 6 components. Among them, the crystallized glass containing lithium oxide as a modification component is especially low in melting point (about 1450-1500° C.) and good in meltability, and, hence, when the glass is molten and molded into a reflector substrate, no special equipment (melting furnace or the like) which can stand high temperatures of higher than 1500° C. is needed and there are less restrictions in production conditions. That is, the reflector substrate can be very simply produced. Furthermore, crystallized glasses containing oxides of alkali metals, such as lithium oxide, sodium oxide and potassium oxide as modification components are better in crystallinity than those containing diphosphorus pentoxide as a modification component. Moreover, crystallized glasses containing niobium oxide or tantalum oxide are good in meltability and besides low in crystallizing temperature and good in crystallinity.

The content of the 6 components in total as modification components is preferably 0.2-5.0 parts by mass, more preferably 0.5-4.6 parts by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility of exerting no effect as modification component, which is not preferred, and if it exceeds the above range, there is the possibility of increase in thermal expansion coefficient, which is not preferred.

The preferred content of lithium oxide is 0.3-0.75 part by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect to improve meltability of the glass by lithium oxide cannot be given, which is undesirable. If the content exceeds the above range, there is the possibility of crystallization being insufficient due to the low crystallinity of the glass, which is undesirable.

The preferred content of diphosphorus pentoxide is 1-3 parts by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect to improve meltability of the glass by diphosphorus pentoxide cannot be given, which is undesirable. If the content exceeds the above range, there is the possibility of crystallization being insufficient due to the low crystallinity of the glass, which is not preferred.

The preferred content of sodium oxide is 0.4-1 part by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect to improve crystallinity of the glass by sodium oxide cannot be obtained, which is not preferred.

The preferred content of potassium oxide is 0.5-1.5 part by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect to improve crystallinity by potassium oxide cannot be exerted, which is not preferred.

The preferred content of niobium oxide is 0.1-0.5 part by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect of improving meltability, lowering crystallizing temperature and improving crystallinity by niobium oxide cannot be exerted, which is not preferred.

The preferred content of tantalum oxide is 0.1-0.5 part by mass based on 100 parts by mass of the main components. If the content is less than the above range, there is the possibility that the effect of improving meltability, lowering crystallizing temperature and improving crystallinity by tantalum oxide cannot be exerted, which is not preferred.

The crystallized glass of the present invention may contain other modification components so long as it contains at least one of the above 6 components as a modification component. For example, it is preferred to contain about 0.1-0.5 part by mass of vanadium oxide (V₂O₅) or molybdenum oxide (MoO₃) as a modification component based on 100 parts by mass of the main components. However, the content of these other modification components should be limited to such a range that the preferred effects of the crystallized glass of the present invention, namely, the effects of having a thermal expansion coefficient of not higher than that of baria-based crystallized glasses and having excellent heat resistance, are not damaged.

An important point in the crystallized glass of the present invention is that when it contains oxides of alkaline earth metals (magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), boron oxide (B₂O₃), yttrium oxide (Y₂O₃), bismuth oxide (Bi₂O₃)) which are generally suitably used as modification components of crystallized glasses, the effect to improve heat resistance is rather reduced. This is because if these components are contained as modification components, since formation of crystalline phase (gahnite, spinel (MgO Al₂O₃), or the like) of high thermal expansion coefficient is readily brought about, thermal expansion coefficient of the glass increases and heat resistance decreases. Particularly, the crystallized glass containing boron oxide as a modification component is more conspicuous in increase of thermal expansion coefficient and decrease of heat resistance. Therefore, it is preferred for the crystallized glass of the present invention to contain substantially no boron oxide as at least a modification component (contain substantially 0% by mass of boron oxide as a modification component).

(4) Additives

The crystallized glass of the present invention may contain additives depending on purpose in addition to the main components, nucleating agent and modification component. For example, addition of antimony oxide (Sb₂O₃) in an amount of about 0.5 part by mass based on 100 parts by mass of the main components as a glass clarifier is preferred in that it can exert the effects to reduce bubbles generated during melting of glass and to allow the bubbles to hardly remain in the glass.

(5) Crystallized Glass

The crystallized glass of the present invention can be obtained by mixing the above-mentioned main components, nucleating agent and modification component at a given ratio to prepare a glass raw material, melting the glass raw material to make a glass, and subjecting the glass to a heat treatment (crystallization treatment) at a high temperature of about 800-900° C. for about 2-4 hours.

The crystallized glass can also be obtained by producing the glass raw material by using, in place of the above main components, nucleating agent and modification component, precursors which can be converted to these components by heating (for example, carbonates, nitrates, and the like), mixing them so as to give a given ratio in terms of oxides to prepare a glass raw material, melting the glass raw material to make a glass, and subjecting the glass to a heat treatment (crystallization treatment) under the similar conditions to those mentioned above.

If the treating temperature and time are less than the above ranges, there is the possibility that crystallization of glass does not sufficiently proceed, resulting in decrease of crystallinity, which is not preferred. If they exceed the above ranges, formation of crystalline phase (gahnite, willemite, or the like) of high thermal expansion coefficient is readily brought about, thermal expansion coefficient of the glass increases, and heat resistance decreases, which is not preferred.

The crystallized glass of the present invention obtained as mentioned above has such characteristic physical properties as high in heat resistance, low in melting point and good in meltability, and, furthermore, is superior in crystal stability with elapse of time under high temperature conditions and extremely small in volumetric contraction even after exposed to high temperatures for a long time.

FIG. 2 is a graph which shows change of volumetric thermal expansion coefficient with elapse of time when the crystallized glasses of the present invention were kept at 600° C., 650° C., 700° C. and 750° C. for each 20 hours. As shown in FIG. 2, the crystallized glasses of the present invention increased in expansion coefficient (expansion of volume) until the temperature of the glasses reached the locking temperature, but after the temperature of the glass reached the locking temperature, they maintained nearly constant expansion coefficient (volume) and hardly changed in expansion coefficient (volume) even after lapse of 20 hours.

On the other hand, when the same test was conducted on lithia-based crystallized glasses, as shown in FIG. 3, after the temperature of the glasses reached the locking temperature and the expansion coefficient (volume) reached the maximum value, the glasses showed a behavior of abrupt decrease of the expansion coefficient (volume). This behavior had the tendency to become conspicuous with increase of the keeping time. That is, lithia-based crystallized glasses show volumetric contraction when they are exposed to high temperatures for a long time.

The reason for the lithia-based crystallized glasses taking such behavior is that the crystalline phase changes with elapse of time because they are kept under high temperature conditions. Specifically, as the reasons, mention may be made of (i) increase of density (contraction of volume) due to growth of crystal grains, (ii) change of the crystalline phase from β-eucryptite solid solution (thermal expansion coefficient ≦0) to β-spodumene solid solution (thermal expansion coefficient ≧0), etc. That is, since the lithia-based crystallized glasses are insufficient in crystal stability with elapse of time under high temperature conditions, they show volumetric contraction upon being exposed to high temperatures for a long time.

Therefore, when a reflector substrate is formed of a lithia-based crystal glass, growth of crystal grains proceeds during long-term use and volumetric contraction occurs, and hence there is the possibility of changing in shape of the reflector substrate. Such change of shape is not desirable because of causing deterioration of reflective characteristics or deviation in condensation point.

Being different from the lithia-based crystallized glass, the crystallized glass of the present invention is less in the above-mentioned defects and, hence, is suitable as a construction material of reflector substrate which is required to have such an endurance as standing the long-term uses of 5000-10000 hours under the high temperature conditions of higher than 600° C. It is needless to say that the crystallized glass of the present invention is a very useful material, considering that recently light source lamps used for illuminators and projector light sources are increased in output and luminance, and thus the reflector substrate tends to be exposed to the higher temperatures.

(6) Reflector Substrate

As already mentioned above, the crystallized glass of the present invention is suitably usable as a reflector substrate constituting a reflector for reflecting light of a light source lamp, particularly, as a constituting material of reflector substrate of illuminators or projector light sources.

The reflector substrate is a member having a concave formed for disposing a reflective film thereon. The concave has no limitation in its shape so long as the desired reflecting characteristics can be obtained when the reflective film is disposed. Usually, the concave is in the form of a rotating second-order surface (e.g., paraboloid, ellipsoid, etc.), and preferred is the ellipsoid which is excellent in condensation efficiency for reflected light.

There are no particular limitations in the construction of the parts other than the concave part, and those of various constructions can be used depending on purpose, and as a general construction, mention may be made of reflector substrate 10 shown in FIG. 4. The reflector substrate 10 shown in FIG. 4 comprises two parts of a bowl-shaped part 14 and a neck part 16. The boundary portion of the bowl-shaped part 14 and the neck part 16 is in the form of constriction to form a constricted part 15. In the bowl-shaped part 14, there is formed a concave 12 for disposing a reflective film therein, and the neck part 16 is provided on the bottom side of the concave 12 in continuity with the bowl-shaped part 14. Furthermore, an inner space 18 is formed by the concave 12 of the bowl-shaped part 14, and at the neck part 16 there is formed a through hole 20 for fitting a light source lamp which opens at the inner space 18 of the bowl-shaped 14.

The above reflector substrate can be produced, for example, by press molding with a mold a molten glass mass (called “gob”) prepared by melting a glass raw material at a high temperature.

As the mold used for molding the reflector substrate, there is used, for example, a reflector substrate molding mold 30 as shown in FIG. 5 which is provided with a mold 32 having a concave portion 32 a having a shape complementary to the outer shape of the reflector substrate 31, a core rod 34 having a convex portion 34 a having a shape complementary to the inner space of the reflector substrate 31, and a ring 36 having a guide hole 36 a guiding the core rod 34 to the concave portion 32 a of the mold 32 and which is constructed so that a cavity 33 for molding the reflector substrate 31 is formed by the mold 32, the core rod 34 and the ring 36 together.

Using the reflector substrate molding mold 30 as mentioned above, the reflector substrate can be molded by the following method. First, a gob 38 is fed from a gob-feeding nozzle 35 ((a) in FIG. 5), and the gob 38 is cut by a cutting blade 37, thereby pouring a given amount of gob 38 into the concave portion 32 a of the mold 32 ((b) in FIG. 5)

Then, the ring 36 is put on the top face of the mold 32, core rod 34 is loosely inserted into the guide hole 36 a of the ring 36, and thereafter the core rod 34 is downwardly pressed ((c)-(e) in FIG. 5). Thus, the core rod 34 is guided to the concave portion 32 a of the mold 32, and simultaneously the mold 32, core rod 34 and ring 36 form together a cavity 33 for molding the reflector substrate 31, and, as a result, it becomes possible to mold the reflector substrate 31 ((f) in FIG. 5). In this case, most of the outer shape of the reflector substrate 31 is molded by the mold 32 having the concave portion 32 a having a shape complementary to the outer shape, and most of the inner space of the reflector substrate 31 is molded by the core rod 34 having the convex portion 34 a having a shape complementary to the shape of the inner space.

After completion of the molding, the reflector substrate 31 is sufficiently cooled, and then first the core rod 34 is pulled up. In this case, since the reflector substrate 31 is pressed downwardly by the ring-36, it is not pulled up together with the core rod 34 and retained inside the mold 32. Then, the ring 36 is pulled up upwardly to disjoint the mold, and the reflector substrate 31 which is a molded product is removed from the mold 32. In this way, the reflector substrate 31 which is a molded product can be obtained.

As shown in FIG. 4 and FIG. 6, a hole is bored on the lower end side of the neck part 16 by mechanical processing or the like to form a through hole 20 for fitting a light source lamp. Then, a reflective film 22 is disposed to cover the concave 12, whereby a reflector can be obtained.

The construction of the reflective film is not particularly limited as long as desired reflecting characteristics can be obtained. For example, there can be suitably used an alternate multilayer film comprising alternately laminated materials of high refractive index such as titania (TiO₂) and those of low refractive index such as silica (SiO₂). Known film forming methods can be used for the formation of the reflective films. In the case of the above alternate multilayer films, a material of high refractive index and a material of low refractive index can be alternately laminated using the conventionally known film forming methods (such as PVD method, CVD method, and sputtering method).

As shown in FIG. 6, a light source lamp 24 such as an ultrahigh pressure mercury lamp is fitted in the through hole 20 for providing light source lamp, this light source lamp 24 is fixed with a fixing material 26 such as heat resistant cement, and furthermore, the opening part of the inner space 18 is closed with a glass-made protective plate 28 (about 4-5 mm thick) to make a light emitting apparatus. The protective plate 28 is provided for inhibiting scattering of broken pieces if the light source lamp is broken upon lapse of life time.

In the above, the present invention has been explained referring to an example of a reflector substrate of a general construction, but it is also a preferred embodiment to use the crystallized glass of the present invention as a constituting material of a reflector substrate provided with a main body having a concave formed for disposing a reflective film and a metallic reticulate body embedded in the main body. That is, a reflector substrate 50 shown in FIG. 7(a)-FIG. 7(c) is preferred which is provided with a main body 17 comprising the crystallized glass of the present invention and having a concave 12 which is a reflecting surface and a metallic reticulate body 52 embedded in the main body 17.

The characteristic construction of the above reflector substrate 50 is that a metallic reticulate body 52 is embedded in the main body of the reflector substrate 50. The reticulate body 52 is provided for inhibiting scattering of broken pieces if the reflector substrate per se is broken upon lapse of life time. Such a reflector substrate is preferred because it can improve safety of light emission apparatus during the use and damages of other devices (for example, liquid crystal projector) attached to the apparatus can be avoided.

The reticulate body 52 must be embedded inside the main body 17 of the reflector substrate 50, and the position of embedding is not particularly limited. Therefore, it may be optionally provided in accordance with the purpose, and usually it is embedded in such a manner that it wraps at least a part of the concave 12 along the concave 12.

The reticulate body 52 must be disposed so that it wraps the concave 12 of the main body 17 along the concave 12, but except for this point, there are no particular limitations in the position of disposing the reticulate body 52. Disposition of the reticulate body 52 to wrap the whole concave 12 as shown in FIG. 7(c) is preferred because the effect to inhibit scattering of broken pieces by the reticulate body 52 is great, but the reticulate body 52 may not necessarily be disposed to wrap the whole concave 12. For example, as shown in FIG. 7(a) and FIG. 7(b), the effect of the present invention can be obtained when at least a part of the concave 12 is wrapped with the reticulate body 52.

In the case of the main body being composed of the two parts of the bowl-shaped part 14 and the neck part 16 as in the reflector substrate 50 shown in FIG. 7(a)-FIG. 7(c), the constriction part 15 which is a boundary portion between the bowl-shaped part 14 and the neck part 16 is a part which is weak against heat stress and readily broken. Therefore, as shown in FIG. 7(a), when the reticulate body 52 is disposed in the vicinity of at least the constriction part 15, the effect can be sufficiently exerted. Furthermore, it is also preferred to dispose the reticulate body 52 continuously from the bowl-shaped part 14 up to the neck part 16 through the constriction part 15 as in the reflector substrate 50 shown in FIG. 7(a)-FIG. 7(c).

The metals constituting the reticulate body are not particularly limited, and it is preferred to select the materials, considering that the main body comprises a crystallized glass.

First, since the reticulate body is embedded in the main body of the reflector substrate, it contacts with a gob of high temperature during production of the reflector substrate. Therefore, it is preferred to select a material excellent in oxidation resistance in order to produce the reflector substrate in an atmospheric environment without carrying out nitrogen purging. Furthermore, since the reflector substrate is used under high temperature conditions, it is preferred to select the material of the reticulate body which has a thermal expansion coefficient close to that of the crystallized glass constituting the main body, a high Young's modulus and an excellent spreadability.

From the above viewpoints, the reticulate body preferably comprises a metal comprising at least one selected from the group consisting of nickel, cobalt, stainless steel and Kovar as a main constituent. By selecting the above metals, it becomes possible to produce the reflector substrate in an atmospheric environment without carrying out nitrogen purging, and breakage of the reflector substrate owing to the difference in thermal expansion behavior between the main body and the reticulate body can be effectively inhibited.

The “main constituent” means that the whole of the reticulate body is not required to be composed of the above metal, but it suffices that the reticulate body is mainly composed of the above metal. Specifically, it means that 30% by mass or more of the metal constituting the reticulate body is the above metal.

Furthermore, since the reflector substrate after molded is subjected to a heat treatment (crystallization treatment) at high temperatures, it is preferred to select a material capable of accelerating the crystallization. From this viewpoint, the reticulate body comprises preferably a metal comprising at least one selected from the group consisting of gold, platinum, silver and copper as a main constituent. These metals are preferred because they can be crystal nuclei of glass and hence can accelerate crystallization of glass and fine the crystals. The same effect can be obtained when the reticulate body has a surface coat comprising the above metal.

The reticulate body must have a network structure, but other constructions can be optionally determined depending on properties of the crystallized glass, size of the reflector substrate and effect to inhibit scattering of broken pieces. For example, the shape of meshes can be square, rhombic, hexagonal, and the like, and the mesh size is suitably about 3-10 mm. The reticulate body is often formed of metal wires having a diameter of about 0.1-1.0 mmφ, and may be formed of metal foils having a width of nearly the same as the above diameter of wires.

The reflector substrate in which the above reticulate body is embedded can be produced in accordance with a method for producing a reflector substrate of general construction as shown in FIG. 5. That is, it may be produced by a method of press molding gob 38 using a reflector substrate molding mold 30 provided with mold 32, core rod 34 and ring 36 as shown in FIG. 8. According to this method, the reflector substrate 50 in which the reticulate body 52 is embedded can be obtained by the same steps as those of the method shown in FIG. 5((b)-(g) in FIG. 8), except that the reticulate body 52 is previously set in the concave part 32 a of the mold 32 before the pouring of gob 38 ((a) in FIG. 8).

EXAMPLE

The crystallized glass of the present invention will be specifically explained using the following examples, which should not be construed as limiting the crystallized glass of the present invention in any manner. The crystallized glasses of examples and comparative examples were evaluated on the four items of heat resistance, crystallinity, meltability and devitrification properties, and overall evaluation was conducted on the basis of the results of the above evaluations. The four items of heat resistance, crystallinity, meltability and devitrification properties were evaluated by the following methods.

[Heat Resistance]

Measurement samples of 3 mm×3 mm×20 mm were cut out from the crystallized glass, and thermal expansion coefficients were measured in the three temperature ranges of 40-400° C., 40-600° C. and 40-800° C. in accordance with the method described in JIS R1618. The heat resistance was evaluated in the following manner. When a crystallized glass having a thermal expansion coefficient at 40-400° C. of not higher than that of lithia-based crystallized glass (not higher than 20×10⁻⁷(/° C.)) was obtained, this is indicated by “0”, when a crystallized glass having a thermal expansion coefficient at 40-400° C. of not higher than that of baria-based crystallized glass (not higher than 45×10⁻⁷ (/° C.)) was obtained, this is indicated by “A”, and when only such a crystallized glass as having a thermal expansion coefficient at 40-400° C. of higher than that of baria-based crystallized glass (higher than 45×10⁻⁷(/° C.)) was obtained, this is indicated by “X”

[Crystallinity]

The crystallinityis shown in the followingmanner. When the minimum temperature at which the glass could be crystallized was lower than 850° C., this is indicated by “◯”, when it was 850-900° C., this is indicated by “Δ”, and when it was higher than 900° C., this is indicated by “x”.

[Meltability]

As for the evaluation of meltability, when the melting temperature of the crystallized glass was lower than 1500° C., this is indicated by “◯”, when it was 1500-1530° C., this is indicated by “Δ”, and when it was higher than 1530° C., this is indicated by “x”.

[Devitrification Properties]

The devitrification properties were evaluated by the frequency of occurrence of devitrification phenomenon when the glass raw material for the crystallized glass was molten to make a molten glass and the molten glass was molded into a shape of the reflector substrate. In the case of producing 100 reflector substrates (samples), when no devitrification phenomenon occurred in any of the samples, this is indicated by “⊚”, when devitrification phenomenon occurred in two or less samples, this is indicated by “◯”, when it occurred in five or less samples, this is indicated by “Δ”, and when it occurred in six or more samples, this is indicated by “X”.

[Overall Evaluation]

As for the overall evaluation on the crystallized glasses of Examples 1-43 and Comparative Examples 1-10, when evaluations on the three items of heat resistance, crystallinity and meltability were all “◯”, this is indicated by “⊚”, when evaluations on two items among the three items were “◯”, this is indicated by “◯”, and other cases are indicated by “Δ”, but when at least one of the heat resistance and the meltability among the three items was evaluated by “X”, the overall evaluation is indicated by “X” irrespective of the above criteria.

As for the overall evaluation on the crystallized glasses of Examples 44-50 and Comparative Examples 11-13, when evaluations on heat resistance, crystallinity and meltability were all “◯” and evaluation on the devitrification properties was “⊚”, this is indicated by “⊚”, when evaluations on heat resistance, crystallinity and meltability were all “◯” and evaluation on the devitrification properties was “◯”, this is indicated by “◯”, and when at least one of the heat resistance and the devitrification properties was evaluated by “Δ”, the overall evaluation is indicated by “Δ”.

Examples 1-8, Comparative Examples 1-4

The main components, the nucleating agent and the modification component described in Table 3 were mixed at the ratio as described in Table 3 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 875° C. or 900° C. for 4 hours to obtain crystallized glasses of Examples 1-8 and Comparative Examples 1-4. Heat resistance, crystallinity and meltability of these crystallized glasses were evaluated and the results are shown in Table 4. TABLE 3 Main component Modification component Total of Total of Total of 6 crystallized Mark components Nucleating agent Glass clarifier P₂O₅ B₂O₃ components glass in (Part by ZrO₂ Sb₂O₃ (Part by (Part by (Part by (Part by mass) (Part by mass) (Part by mass) mass) mass) mass) mass) Exam. 1 (I) 100 5 0.5 1 — 1 106.5 Exam. 2 (I) 100 5 0.5 3 — 3 108.5 Compar. Exam. 1 (I) 100 5 0.5 — 1 — 106.5 Compar. Exam. 2 (I) 100 5 0.5 — 3 — 108.5 Exam. 3 (I) 100 5 0.5 1 1 1 107.5 Exam. 4 (I) 100 5 0.5 2 2 2 109.5 Compar. Exam. 3 (II) 100 4 0.5 — — — 104.5 Exam. 5 (II) 100 4 0.5 1 — 1 105.5 Exam. 6 (II) 100 4 0.5 2 — 2 106.5 Compar. Exam. 4 (II) 100 3 0.5 — — — 103.5 Exam. 7 (II) 100 3 0.5 1 — 1 104.5 Exam. 8 (II) 100 3 0.5 2 — 2 105.5

TABLE 4 Crystallizing temp. 875° C. Crystallizing temp. 900° C. Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × Evaluation 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) Heat Overall 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. resistance Crystallinity Meltability evaluation Exam. 1 — — — 1.5 2.4 3.9 ◯ Δ Δ Δ Exam. 2 28.4 uncalcu- — — — — Δ Δ Δ Δ lable Compar. 33.3 35.9 38.7 — — — Δ Δ X X Exam. 1 Compar. 45.1 46.3 47.5 — — — X Δ X X Exam. 2 Exam. 3 31.3 uncalcu- — — — — Δ Δ Δ Δ Exam. 4 44.9 lable 44.5 — — — Δ Δ Δ Δ Compar. −5.7 −2.7 — −7.1 −3.0 −0.1 ◯ ◯ X X Exam. 3 Exam. 5 5.4 8.4 — 6.2 9.0 — ◯ ◯ Δ ◯ Exam. 6 27.5 29.2 — 28.3 29.0 — Δ X Δ Δ Compar. — — — 9.5 9.2 — ◯ Δ X X Exam. 4 Exam. 7 27.1 28.9 — — — — Δ Δ Δ Δ Exam. 8 25.3 27.7 — 27.8 28.4 — Δ X Δ Δ In Column of average linear thermal expansion coefficient, “uncalculable” shows that the calculation was impossible due to the presence of transition point and yielding point on thermal expansion curve.

[Evaluation]

As shown in Table 3 and Table 4, the crystallized glasses of Examples 1-8 containing diphosphorus pentoxide as a modification component were superior in meltability to those of Comparative Examples 1-4 containing no diphosphorus pentoxide as a modification component. Particularly, the crystallized glass of Example 5 which did not contain boron oxide and contained only 1 part by mass of diphosphorus pentoxide as a modification component was superior in both heat resistance and crystallinity and thus showed further better results. On the other hand, the crystallized glass of Comparative Example 2 containing boron oxide as a modification component in a relatively large amount, namely, 3 parts by mass, was inferior in both heat resistance and meltability.

Examples 9-19

The main components, the nucleating agent and the modification component described in Table 5 were mixed at the ratio as described in Table 5 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 825° C., 850° C., 875° C. or 900° C. for 4 hours to obtain crystallized glasses of Examples 9-19. Heat resistance, crystallinity and meltability of these crystallized glasses were evaluated and the results are shown in Table 6. TABLE 5 Main component Nucleating Glass Modification component Total of Total of agent clarifier Total of 6 crystallized Mark components ZrO₂ Sb₂O₃ P₂O₅ Li₂O Na₂O K₂O Cs₂O components glass in (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) Exam. 9 (VII) 100 5 0.5 — 0.5 — — — 0.5 106.0 Exam. 10 (VII) 100 5 0.5 — — 0.5 — — 0.5 106.0 Exam. 11 (I) 100 5 0.5 — 0.5 — — — 0.5 106.0 Exam. 12 (I) 100 5 0.5 — — 0.5 — — 0.5 106.0 Exam. 13 (I) 100 5 0.5 — — — 0.5 — 0.5 106.0 Exam. 14 (I) 100 5 0.5 — — — — 0.5 0.5 106.0 Exam. 15 (I) 100 5 0.5 — 0.3 0.4 0.6 — 1.3 106.8 Exam. 16 (I) 100 5 0.5 1 0.3 0.4 0.6 — 2.3 107.8 Exam. 17 (I) 100 5 0.5 1 0.45 0.6 0.9 — 2.95 108.45 Exam. 18 (I) 100 5 0.5 1 0.6 0.8 1.2 — 3.6 109.1 Exam. 19 (I) 100 5 0.5 1 0.75 1 1.5 — 4.25 109.75

TABLE 6 Crystallizing temp. 850° C. Crystallizing temp. 875° C. Crystallizing temp. 900° C. Average linear thermal Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × expansion coefficient × 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. Exam. 9 — — — −18.2 — — −12.3 −12.5 −11.1 Exam. 10 — — — — — 4.5 4.6 5.1 Exam. 11 −5.4 −4.8 −4.6 −4.2 −4.0 −3.9 5.1 3.5 — Exam. 12 22.3 uncalcu- — 6.3 5.8 6.1 28.4 26.5 — lable Exam. 13 29.2 uncalcu- — 7.9 8.1 — 24.1 24.7 — lable Exam. 14 19.6 incalcu- — −2.7 −0.9 0.5 −2.9 −2.0 — lable Exam. 15 24.8 uncalcu- — 4.1 4.9 7.1 2.6 3.4 5.0 lable Exam. 16 25.0 uncalcu- — 7.6 8.0 10.1 5.4 5.7 6.6 lable Exam. 17 19.3 21.1 28.0 11.5 12.3 19.1 — — — Exam. 18 15.5 16.9 23.6 9.9 11.6 17.5 — — — Exam. 19 16.8 18.4 27.2 15.6 16.5 24.5 — — — Evaluation Overall Heat resistance Crystallinity Meltability evaluation Exam. 9 ◯ Δ Δ Δ Exam. 10 ◯ Δ Δ Δ Exam. 11 ◯ ◯ Δ ◯ Exam. 12 ◯ Δ Δ Δ Exam. 13 ◯ Δ Δ Δ Exam. 14 ◯ ◯ Δ ◯ Exam. 15 ◯ ◯ Δ ◯ Exam. 16 ◯ ◯ Δ ◯ Exam. 17 ◯ ◯ ◯ ⊚ Exam. 18 ◯ ◯ ◯ ⊚ Exam. 19 ◯ ◯ ◯ ⊚ In Column of average linear thermal expansion coefficient, “uncalculable” shows that the calculation was impossible due to the presence of transition point and yielding point on thermal expansion curve.

[Evaluation]

As shown in Table 5 and Table 6, the crystallized glass of Example 11 having a main component constitutional ratio indicated by mark (I) in FIG. 1 was superior in crystallinity to the crystallized glass of Example 9 having a main component constitutional ratio indicated by mark (VII) in FIG. 1. Among the crystallized glasses of Examples 11-19 having a main component constitutional ratio indicated by mark (I) in FIG. 1, those of Examples 11, 14, 15 and 16 containing lithium oxide or cesium oxide as a modification component were superior in crystallinity to those of Examples 12 and 13 containing only sodium oxide or potassium oxide. Furthermore, the crystallized glasses of Examples 17-19 in which the total amount of the modification components (6 components) specified in the present invention exceeded 2.5 part by mass were additionally superior in meltability and showed markedly good results.

Comparative Examples 5-10

The main components, the nucleating agent and the modification component described in Table 7 were mixed at the ratio as described in Table 7 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 875° C. or 900° C. for 4 hours to obtain crystallized glasses of Comparative Examples 5-10. Heat resistance, crystallinity and meltability of these crystallized glasses were evaluated and the results are shown in Table 8. TABLE 7 Main Component Total of Nucleating Glass Modification component Total of main agent clarifier Bi₂O₃ CaO SrO MgO BaO Y₂O₃ Total of 6 crysallized Mark components ZrO₂ Sb₂O₃ (Part (Part (Part (Part (Part (Part components glass in (Part by (Part by (Part by by by by by by by (Part by (Part by mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) Compar. Exam. 5 (VII) 100 5 0.5 2 — — — — — — 107.5 Compar. Exam. 6 (VII) 100 5 0.5 — 2 — — — — — 107.5 Compar. Exam. 7 (VII) 100 5 0.5 — — 2 — — — — 107.5 Compar. Exam. 8 (VII) 100 5 0.5 — — — 2 — — — 107.5 Compar. Exam. 9 (VII) 100 5 0.5 — — — — 2 — — 107.5 Compar. Exam. 10 (VII) 100 5 0.5 — — — — — 2 — 107.5

TABLE 8 Crystallizing temp. 875° C. Crystallizing temp. 900° C. Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × Evaluation 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) Heat Overall 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. resistance Crystallinity Meltability evaluation Compar. 32.8 35.6 — 50.5 50.6 — Δ Δ X X Exam. 5 Compar. 33.3 36.4 — 27.5 26.9 — Δ X X X Exam. 6 Compar. 31.6 34.3 — — — — Δ X X X Exam. 7 Compar. 32.6 35.6 — — — — Δ X X X Exam. 8 Compar. 30.1 33.1 — — — — Δ X X X Exam. 9 Compar. 31.9 34.6 — 38.4 41.3 44.4 Δ Δ X X Exam. 10

[Evaluation]

As shown in Table 7 and Table 8, the crystallized glasses of Comparative Examples 5-10 containing bismuth oxide, calcium oxide, strontium oxide, magnesium oxide, barium oxide or yttrium oxide as a modification component in place of the modification components (6 components) specified in the present invention were inferior in meltability.

Examples 20-29

The main components, the nucleating agent and the modification component described in Table 9 were mixed at the ratio as described in Table 9 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 800° C., 825° C. or 850° C. for 4 hours to obtain crystallized glasses of Examples 20-29. Heat resistance, crystallinity and meltability of these crystallized glasses were evaluated and the results are shown in Table 10. TABLE 9 Main component Modification component Total of Nucleating Glass Total of Total of main agent clarifier P₂O₅ V₂O₅ Nb₂O₅ Ta₂O₅ MoO₃ Li₂O Na₂O K₂O 6 com- crystal- Mark components ZrO₂ Sb₂O₃ (Part (Part (Part (Part (Part (Part (Part (Part ponents lized glass in (Part (Part (Part by by by by by by by by (Part (Part by mass) by mass) by mass) mass) mass) mass) mass) mass) mass) mass) mass) by mass) by mass) Exam. 20 (I) 100 5 0.5 1 0.2 — — — 0.6 0.8 1.2 3.6 109.3 Exam. 21 (I) 100 5 0.5 1 — 0.2 — — 0.6 0.8 1.2 3.8 109.3 Exam. 22 (I) 100 5 0.5 1 — — 0.2 — 0.6 0.8 1.2 3.8 109.3 Exam. 23 (I) 100 5 0.5 1 — — — 0.2 0.6 0.8 1.2 3.6 109.3 Exam. 24 (I) 100 4 0.5 1 — 0.3 — — 0.6 0.8 1.2 3.9 108.4 Exam. 25 (I) 100 4 0.5 1 — 0.5 — — 0.6 0.8 1.2 4.1 108.6 Exam. 26 (I) 100 3 0.5 1 — 0.5 — — 0.6 0.8 1.2 4.1 107.6 Exam. 27 (I) 100 4 0.5 1 — — 0.1 — 0.6 0.8 1.2 3.7 108.2 Exam. 28 (I) 100 4 0.5 1 — — 0.3 — 0.6 0.8 1.2 3.9 108.4 Exam. 29 (I) 100 4 0.5 1 — — 0.5 — 0.6 0.8 1.2 4.1 108.6

TABLE 10 Crystallizing temp. 800° C. Crystallizing temp. 825° C. Crystallizing temp. 850° C. average linear thermal average linear thermal average linear thermal expansion coefficient × expansion coefficient × expansion coefficient × 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. Exam. 20 36.6 uncalcu- — 15.3 16.8 25.1 — — — lable Exam. 21 18.2 19.8 22.7 12.6 13.2 19.5 — — — Exam. 22 30.2 uncalcu- — 14.0 15.3 21.8 — — — lable Exam. 23 35.0 uncalcu- — 16.6 18.1 26.9 — — — lable Exam. 24 — — — 15.7 16.3 25.1 15.1 15.7 24.3 Exam. 25 — — — 14.7 15.4 22.8 14.1 15.5 21.3 Exam. 26 — — — 29.7 uncalcu- — 10.6 12.2 — lable Exam. 27 — — — — — — 14.8 16.3 23.8 Exam. 28 — — — 13.5 14.6 — 13.9 14.6 21.7 Exam. 29 — — — 12.5 13.0 19.8 13.0 14.4 19.8 Evaluation Overall Heat resistance Crystallinity Meltability evaluation Exam. 20 ◯ Δ ◯ ◯ Exam. 21 ◯ ◯ ◯ ⊚ Exam. 22 ◯ Δ ◯ ◯ Exam. 23 ◯ Δ ◯ ◯ Exam. 24 ◯ ◯ ◯ ⊚ Exam. 25 ◯ ◯ ◯ ⊚ Exam. 26 ◯ ◯ ◯ ⊚ Exam. 27 ◯ ◯ ◯ ⊚ Exam. 28 ◯ ◯ ◯ ⊚ Exam. 29 ◯ ◯ ◯ ⊚ In Column of average linear thermal expansion coefficient, “uncalculable” shows that the calculation was impossible due to the presence of transition point and yielding point on thermal expansion curve.

Example 30-43

The main components, the nucleating agent and the modification component described in Table 11 were mixed at the ratio as described in Table 11 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 825° C. or 850° C. for 4 hours to obtain crystallized glasses of Examples 30-43. Heat resistance, crystallinity and meltability of these crystallized glasses were evaluated and the results are shown in Table 12. TABLE 11 Main Component Total of Total of Nucleating Glass Modification component crystal- main agent clarifier P₂O₅ Nb₂O₅ Ta₂O₅ Li₂O Na₂O K₂O Total of 6 lized Mark components ZrO₂ Sb₂O₃ (Part (Part (Part (Part (Part (Part components glass in (Part (Part (Part by by by by by by (Part (Part by mass) by mass) by mass) mass) mass) mass) mass) mass) mass) by mass) by mass) Exam. 30 (I) 100 4 0.5 1 0.1 0.1 0.6 0.8 1.2 3.8 108.3 Exam. 31 (I) 100 4 0.5 1 0.3 0.3 0.6 0.8 1.2 4.2 108.7 Exam. 32 (I) 100 4 0.5 1 0.5 0.5 0.6 0.8 1.2 4.6 109.1 Exam. 33 (I) 100 5 0.5 1 0.1 0.1 0.6 0.8 1.2 3.8 109.3 Exam. 34 (I) 100 5 0.5 1 0.2 0.2 0.6 0.8 1.2 4.0 109.5 Exam. 35 (I) 100 5 0.5 1 0.3 0.3 0.6 0.8 1.2 4.2 109.7 Exam. 36 (I) 100 5 0.5 1 0.5 0.5 0.6 0.8 1.2 4.6 110.1 Exam. 37 (I) 100 5 0.5 1 0.1 0.1 0.45 0.6 0.9 3.15 108.7 Exam. 38 (I) 100 5 0.5 1 0.2 0.2 0.45 0.6 0.9 3.35 108.9 Exam. 39 (I) 100 5 0.5 1 0.3 0.3 0.45 0.6 0.9 3.55 109.1 Exam. 40 (I) 100 5 0.5 1 0.5 0.5 0.45 0.6 0.9 3.95 109.5 Exam. 41 (I) 100 4.5 0.5 1 0.1 0.1 0.6 0.7 1 3.5 108.5 Exam. 42 (I) 100 4.5 0.5 1 0.3 0.2 0.6 0.7 1 3.8 108.8 Exam. 43 (I) 100 4.5 0.5 1 0.5 0.5 0.6 0.7 1 4.3 109.3

TABLE 12 Crystallizing temp. 825° C. Crystallizing temp. 850° C. Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × Evaluation 10⁻⁷ (/° C.) 10⁻⁷ (/° C.) Heat Overall 40-400° C. 40-600° C. 40-800° C. 40-400° C. 40-600° C. 40-800° C. resistance Crystallinity Meltability evaluation Exam. 30 12.9 13.8 — 12.0 12.9 — ◯ ◯ ◯ ⊚ Exam. 31 14.0 15.7 23.2 12.6 13.2 20.7 ◯ ◯ ◯ ⊚ Exam. 32 13.8 15.4 22.6 13.1 14.6 20.9 ◯ ◯ ◯ ⊚ Exam. 33 12.3 13.5 18.8 13.3 14.6 19.2 ◯ ◯ ◯ ⊚ Exam. 34 12.6 13.2 18.6 10.8 10.9 — ◯ ◯ ◯ ⊚ Exam. 35 12.9 14.1 18.8 11.3 12.3 16.1 ◯ ◯ ◯ ⊚ Exam. 36 9.9 10.5 15.0 11.4 11.7 15.1 ◯ ◯ ◯ ⊚ Exam. 37 — — — 7.8 7.9 11.4 ◯ ◯ ◯ ⊚ Exam. 38 — — — 7.8 8.4 — ◯ ◯ ◯ ⊚ Exam. 39 — — — 8.3 9.2 12.1 ◯ ◯ ◯ ⊚ Exam. 40 — — — 8.4 9.4 12.5 ◯ ◯ ◯ ⊚ Exam. 41 — — — 10.4 10.5 — ◯ ◯ ◯ ⊚ Exam. 42 — — — 9.6 10.6 13.9 ◯ ◯ ◯ ⊚ Exam. 43 — — — 10 11.2 14.6 ◯ ◯ ◯ ⊚

[Evaluation]

As shown in Table 9-Table 12, the crystallized glasses of Examples 21 and 24-43 containing niobium oxide or tantalum oxide in addition to alkali metal oxides as modification components were superior in all of heat resistance, crystallinity and meltability and showed very good results. Furthermore, the crystallized glasses of Examples 20 and 23 containing vanadium oxide or molybdenum oxide in addition to alkali metal oxides as modification components also showed good results, but were somewhat inferior in crystallinity as compared with the crystallized glasses of Examples 21 and 24-43 which showed very good results.

Examples 44-50 and Comparative Examples 11-13

The main components, the nucleating agent and the modification component described in Table 13 were mixed at the ratio as described in Table 13 to prepare a glass raw material, this glass raw material was molten to make a glass, and the resulting glass was subjected to a heat treatment (crystallizing treatment) at 800° C. or 825° C. for 4 hours to obtain crystallized glasses of Examples 44-50 and Comparative Examples 11-13. Heat resistance, crystallinity, meltability and devitrification properties of these crystallized glasses were evaluated and the results are shown in Table 14. TABLE 13 Main component Total of Total of Glass Modification component crystal- main Nucleating agent clarifier Total of 6 lized Mark components ZrO₂ SnO₂ Sb₂O₃ P₂O₅ Nb₂O₅ Ta₂O₅ Li₂O Na₂O K₂O components glass in (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by (Part by mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) mass) Exam. 44 (I) 100 4 — 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 108.7 Exam. 45 (I) 100 4 0.5 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 109.2 Exam. 46 (I) 100 4 1 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 109.7 Exam. 47 (I) 100 4 1.5 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 110.2 Exam. 48 (I) 100 4 2 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 110.7 Exam. 49 (I) 100 3 1.5 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 109.2 Exam. 50 (I) 100 3 2 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 109.7 Compar. (I) 100 — 4 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 108.7 Exam. 11 Compar. (I) 100 — 5 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 109.7 Exam. 12 Compar. (I) 100 — 6 0.5 1 0.3 0.2 0.6 0.9 1.2 4.2 110.7 Exam. 13

TABLE 14 Crystallizing temp. 800° C. Crystallizing temp. 825° C. Average linear thermal Average linear thermal expansion coefficient × expansion coefficient × 10⁻⁷ (/° C.) Crystalline 10⁻⁷ (/° C.) Crystalline 40-400° C. 40-600° C. 40-800° C. phase 40-400° C. 40-600° C. 40-800° C. phase Exam. 44 17.2 18.6 28.4 Qu 15.4 16.3 22.3 Qu Exam. 45 — — — — 13.3 14.8 21.6 — Exam. 46 — — — — 16.1 18.6 24.8 — Exam. 47 — — — — 15.0 16.9 22.9 — Exam. 48 — — — — 13.8 16.1 21.8 — Exam. 49 — — — — 17.6 20.5 27.7 — Exam. 50 9.9 10.5 15.0 — 14.5 17.0 22.3 Pe(Qu) Compar. 34.9 39.0 uncalcu- — 7.8 7.9 11.4 Qu(Ga, Wi) Exam. 11 lable Compar. 32.5 34.7 43.7 — 34.8 36.4 41.8 Qu(Ga, Wi) Exam. 12 Compar. 36.4 38.7 — — 33.6 35.0 — Qu(Ga, Wi) Exam. 13 Evaluation devitrification Overall Heat resistance Crystallinity Meltability properties evaluation Exam. 44 ◯ ◯ ◯ Δ Δ Exam. 45 ◯ ◯ ◯ Δ Δ Exam. 46 ◯ ◯ ◯ Δ Δ Exam. 47 ◯ ◯ ◯ Δ Δ Exam. 48 ◯ ◯ ◯ Δ Δ Exam. 49 ◯ ◯ ◯ ◯ ◯ Exam .50 ◯ ◯ ◯ ⊚ ⊚ Compar. ◯ ◯ ◯ ⊚ ⊚ Exam. 11 Compar. Δ ◯ ◯ ⊚ Δ Exam. 12 Compar. Δ ◯ ◯ Δ Δ Exam. 13 In Column of crystalline phase, the bold letters means main crystalline phase and letters in parentheses indicate other crystalline phases, and Qu: β-quartz solid solution, Pe: zinc-petallite solid solution, Wi: willemite, and Ga: gahnite. In Column of average linear thermal expansion coefficient, “uncalculable” shows that the calculation was impossible due to the presence of transition point and yielding point on thermal expansion curve.

[Evaluation]

As shown in Table 13-Table 14, the crystallized glass of Example 44 containing only 4 parts by mass of zirconia as a nucleating agent was superior in all of heat resistance, crystallinity and meltability and showed very good results like the crystallized glasses of Examples 17-19, 21 and 24-43, but when devitrification properties were examined, devitrification phenomenon caused by recrystallization of zirconia as a nucleating agent was seen in a part of the samples.

The crystallized glasses of Examples 45-48 which corresponded to the crystallized glass of Example 44 to which merely tin dioxide was added as a nucleating agent without changing the content of zirconia were not improved in devitrification properties.

On the other hand, the crystallized glass of Example 49 in which the content of zirconia as the nucleating agent was reduced to 3 parts by mass and instead 1.5 parts by mass of tin dioxide as a nucleating agent was contained was improved in devitrification properties and was not deteriorated in crystallinity. That is, in the case of the crystallized glass of Example 49, recrystallization of zirconia at the steps of melting and molding of the glass raw material could be inhibited with maintaining good crystallinity.

Furthermore, the crystallized glass of Example 50 in which the content of zirconia as a nucleating agent was reduced to 3 parts by mass and instead 2 parts by mass of tin dioxide as a nucleating agent was contained was markedly improved in devitrification properties and was not deteriorated in crystallinity. That is, in the case of the crystallized glass of Example 50, recrystallization of zirconia at the steps of melting and molding of the glass raw material could be inhibited with maintaining good crystallinity. Moreover, since its main crystalline phase was zinc petallite solid solution, it was low in thermal expansion coefficient and had excellent heat resistance comparable to that of lithia-based crystallized glass.

Furthermore, when tin dioxide as a nucleating agent was contained in place of the whole of zirconia as a nucleating agent (namely, only tin dioxide as a nucleating agent was contained), devitrification properties could be markedly improved with maintaining good crystallinity and heat resistance in some samples as in the case of the crystallized glass of Comparative Example 11, but, in some cases, thermal expansion coefficient of crystallized glass per se increased to deteriorate heat resistance due to the formation of gahnite or willemite as in the cases of the crystallized glasses of Comparative Examples 12 and 13. Moreover, in the crystallized glass of Comparative Example 13 in which the content of tin dioxide was 6 parts by mass, devitrification phenomenon occurred as in the case of zirconia because tin dioxide per se was readily recrystallized.

[Stability of Crystal with Elapse of Time]

Apart from evaluation of the heat resistance, crystallinity, meltability and devitrification properties mentioned above, evaluation of stability of crystal with elapse of time was conducted. Evaluation of stability of crystal with elapse of time was conducted in the following manner. Measurement samples of 0.3 mm×3 mm×20 mmwere cutout from the crystallized glass, and were kept under high temperatures of 600° C., 650° C., 700° C. and 750° C. for 20 hours, and change of volume expansion coefficient with elapse of time was measured in accordance with the method described in JIS R1618. The subjects evaluated were the crystallized glass of Example 50 and commercially available lithia-based crystallized glass of which main crystalline phases were β-spodumene solid solution and β-eucryptite solid solution (referred to as “Comparative Example 14”). The crystallized glass of Comparative Example 14 had the composition as described in Table 15. The results are shown in FIG. 2 and FIG. 3. TABLE 15 Crystallizing Temperature 900° C. Constitutional component ratio Average linear thermal (100% by mass in total) expansion coefficient × Li₂O Al₂O₃ SiO₂ 10⁻⁷ (/° C.) Crystalline (% by mass) (% by mass) (% by mass) 40-400° C. 40-600° C. 40-700° C. phase Comparative 6.0 32.0 62.0 17.0 24.0 34.0 Eu, Sp Example 14 In Column of crystalline phase, the bold letters means main crystalline phase, and Eu: β-eucryptite solid solution, and Sp: β-spodumene solid solution.

As can be seen from the graph of FIG. 2, the crystallized glass of Example 50 increased in expansion coefficient (expansion of volume) with increase of temperature until the glass temperature reached the locking temperature, but maintained nearly a constant expansion coefficient (volume) after the glass temperature reached the locking temperature, which did not substantially changed even after lapse of 20 hours. That is, the crystallized glass of Example 50 was high in stability with elapse of time under high temperature conditions and showed substantially no change in contraction of volume even after exposed to high temperature for a long time.

On the other hand, as shown in FIG. 3, after the crystallized glass of Comparative Example 14 reached the locking temperature and the expansion coefficient (volume) reached the maximum value, the crystallized glass showed a behavior of abrupt decrease in expansion coefficient (decrease of volume). This behavior had the tendency to become conspicuous with increase of the locking temperature. That is, the crystallized glass of Comparative Example 14 showed contraction of volume when it was exposed to high temperatures for a long time. Specifically, the crystallized glass of Example 50 showed a contraction of volume of 0% by volume after lapse of 20 hours at 750° C. while the crystallized glass of Comparative Example 14 showed a contraction of volume of 0.5% by volume.

INDUSTRIAL APPLICABILITY

The zinc oxide-alumina-silica-based crystallized glass of the present invention is suitably usable as a reflector substrate which constitutes a reflector for reflecting lights of light source lamps, particularly, as a reflector substrate of illuminators or projector light sources. 

1. A zinc oxide-alumina-silica-based crystallized glass containing zinc oxide (ZnO), alumina (Al₂O₃) and silica (SiO₂) as main components, and zirconia (ZrO₂) as a nucleating agent, wherein the main components comprise 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica and the main components amount to 100% by mass in total, the nucleating agent is contained in an amount of 3-6 parts by mass based on 100 parts by mass of the main components, and at least one component selected from the group consisting of lithium oxide (Li₂O), sodium oxide (Na₂O), potassium oxide (K₂O), diphosphorus pentoxide (P₂O₅), niobium oxide (Nb₂O₅) and tantalum oxide (Ta₂O₅) is contained as a modification component in addition to the main components and the nucleating agent.
 2. A zinc oxide-alumina-silica-based crystallized glass according to claim 1, wherein a crystalline phase is constituted of the main components and the main crystalline phase is zinc petallite (Zn-petallite) solid solution or β-quartz solid solution.
 3. A zinc oxide-alumina-silica-based crystallized glass according to claim 1, wherein at least one component selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, diphosphorus pentoxide, niobium oxide and tantalum oxide is contained as a modification component in a total amount of 0.2-5.0 parts by mass based on 100 parts by mass of the main components.
 4. A zinc oxide-alumina-silica-based crystallized glass according to claim 1, wherein tin dioxide (SnO₂) is contained as a nucleating agent in place of a part of zirconia as the nucleating agent, and the content of tin dioxide is 0.5-4 parts by mass based on 100 parts by mass of the main components.
 5. A reflector substrate which comprises a zinc oxide-alumina-silica-based crystallized glass containing zinc oxide (ZnO), alumina (Al₂O₃) and silica (SiO₂) as main components, and zirconia (ZrO₂) as a nucleating agent, wherein the main components comprise 20-30% by mass of zinc oxide, 15-25% by mass of alumina and 50-60% by mass of silica and the main components amount to 100% by mass in total, the nucleating agent is contained in an amount of 3-6 parts by mass based on 100 parts by mass of the main components, and at least one component selected from the group consisting of lithium oxide (Li₂O), sodium oxide (Na₂O), potassium oxide (K₂O), diphosphorus pentoxide (P₂O₅), niobium oxide (Nb₂O₅) and tantalum oxide (Ta₂O₅) is contained as a modification component in addition to the main components and the nucleating agent, and wherein the reflector substrate has a main body having a concave for disposing a reflective film therein and a metallic reticulate body embedded in the main body.
 6. A reflector substrate according to claim 5, wherein the reticulate body comprises a metal containing as a main component at least one metal selected from the group consisting of nickel (Ni), cobalt (Co), stainless steel (SUS: Steel Use Stainless) and kobar.
 7. A reflector substrate according to claim 5, wherein the reticulate body comprises a metal containing as a main component at least one metal selected from the group consisting of gold (Au), platinum (Pt), silver (Ag) and copper (Cu) or has a surface film comprising the above metal.
 8. A zinc oxide-alumina-silica-based crystallized glass according to claim 2, wherein at least one component selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, diphosphorus pentoxide, niobium oxide and tantalum oxide is contained as a modification component in a total amount of 0.2-5.0 parts by mass based on 100 parts by mass of the main components.
 9. A reflector substrate according to claim 6, wherein the reticulate body comprises a metal containing as a main component at least one metal selected from the group consisting of gold (Au), platinum (Pt), silver (Ag) and copper (Cu) or has a surface film comprising the above metal. 